CN106925349A - A kind of solid supported type metal porphyrin catalyst and its application in terms of maleic acid is prepared - Google Patents

A kind of solid supported type metal porphyrin catalyst and its application in terms of maleic acid is prepared Download PDF

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CN106925349A
CN106925349A CN201710164332.7A CN201710164332A CN106925349A CN 106925349 A CN106925349 A CN 106925349A CN 201710164332 A CN201710164332 A CN 201710164332A CN 106925349 A CN106925349 A CN 106925349A
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catalyst
reaction
type metal
maleic acid
supported type
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CN106925349B (en
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王海军
黄义
吴春炎
袁文文
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Jiangnan University
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Jiangnan University
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Priority to PCT/CN2017/113868 priority patent/WO2018171251A1/en
Priority to US16/201,087 priority patent/US10525454B2/en
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    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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    • B01J29/42—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing iron group metals, noble metals or copper
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Abstract

The invention discloses a kind of solid supported type metal porphyrin catalyst and its application in terms of maleic acid is prepared, belong to catalysis of metalloporphyrin applied technical field.Solid supported type metal porphyrin catalyst of the invention prepares maleic acid for being catalyzed furfural, and with good catalytic effect, and reaction condition is gentle, the energy consumption needed for greatly reducing prior art.Catalyst of the invention can provide a good microenvironment for reaction, so as to improve the yield and selectivity of maleic acid；According to the method for the present invention, the conversion ratio of furfural is 20.4% 95.6%, and the yield of maleic acid is 10% 56.1%, and selectivity is 43.6% 76.1%.Meanwhile, catalyst is easily isolated, can recycled for multiple times, environmental protection.

Description

A kind of solid supported type metal porphyrin catalyst and its application in terms of maleic acid is prepared
Technical field
The present invention relates to a kind of solid supported type metal porphyrin catalyst and its application in terms of maleic acid is prepared, belong to metal Porphyrin catalytic applications technical field.
Background technology
In the past few decades, human society is developed rapidly, and up-to-dateness is improved constantly, but at the same time, the energy It is also increasingly serious with environmental problem, the need for traditional fossil energy has been difficult supply industrial development, global warming, the three wastes, mist The problems such as haze, even more constantly threatens the health of the mankind.Therefore, cleaning is found and the reproducible energy replaces traditional fossil The energy is extremely urgent.Biomass receive increasing researcher as most commonly used regenerative resource is distributed on the earth Concern, the report that high added value platform chemicals are prepared by biomass-based raw material is also more and more, so developing Biomass energy has a extensive future, very with meaning.
Used as biomass-based five carbon compound of one kind, furfural is derived among the agricultural by products such as corn, wheat, wood chip, These feed distributions are extensive, and renewable, and the energy reserve of the mankind can't be threatened using them.Can be with by furfural Synthesize many platform chemicals, wherein just including a kind of important high added value intermediate-maleic acid, it can be as tree The synthesis material of the products such as fat, coating, additive, plasticizer, medicine, is widely used in industrial production industry.
But the current industrial production line still with Oxybenzene under HTHP or butane as maleic acid, use or stone Oil derives traditional fossil energy, and reaction condition is harsher, so all being brought to the energy and economic aspect very big Burden.Constantly there is report with furfural as Material synthesis maleic acid to occur in recent years, but in these reports preparation method reaction Condition is still harsher, is much required for being carried out under the reaction temperature higher than 100 DEG C or the reaction pressure more than 2MPa, and The catalyst for being used is confined to the catalyst of heteropoly acid type and vanadium type.Have been reported that with H3PMo12O40+Cu(NO3)2It is catalysis System, the catalysis oxidation furfural under the oxygen pressure of 2MPa, after 14h, the yield of maleic acid is 49%, although the conversion ratio of furfural It is 95%, but the selectivity of maleic acid is relatively low, is 52%, and side reaction phenomenon is more serious.Also have been reported that double in water/organic solvent In phase system, individually with H3PMo12O40·xH2O prepares maleic acid for catalyst furfural, after 14h is reacted, although Malaysia The selectivity of acid has and improves to a certain degree, but yield only has 35%.Prepared maleic acid yield reported above and selectivity It is all not high enough, and have a serious defect, be exactly not gentle enough reaction condition, the pressure ratio of oxygen is higher, reaction when Between it is also very long, considerably increase reaction needed for energy consumption.
The content of the invention
It is a kind of with efficient catalytic capability present invention aim at synthesis in order to overcome the shortcoming and defect of prior art Solid supported type metal porphyrin catalyst, for the conversion of furfural to maleic acid.The method for preparing catalyst easily, gentle anti- There is good catalytic effect under the conditions of answering, and be easily recycled, embody the objective of Green Sustainable.
Inventor has synthesized the ferriporphyrin with different substituents group first, when they are directly used in catalytic reaction, though So the conversion ratio of furfural under certain condition can reach more than 90%, but the selectivity of maleic acid only has 50% or so, and when After they are combined with the molecular sieve carrier with special space structure, under the optimum reaction condition for being optimized, the product of maleic acid Rate is 56%, and selectivity is also up to 76%, meanwhile, reaction is carried out under the reaction pressure of 1MPa, and the reaction time also only has 6h, phase More gentle for above-mentioned report reaction condition, so as to reduce energy consumption of reaction, and reaction system is heterogeneous, and reaction terminates Catalyst can be isolated by simple filtering afterwards, by washing, after drying, it is separated go out the catalysis of solid supported type metal porphyrin Agent can put into again next time when using, by five loop tests, the yield of maleic acid is still 55% or so, and catalytic performance is several Do not change, therefore the catalyst has environmental protection, the characteristics of economical and practical, has great application prospect.
First purpose of the invention is to provide a kind of method that catalysis oxidation furfural prepares maleic acid, and methods described is profit Solid supported type metal porphyrin catalyst is used, furfural is substrate, oxygen as oxidant, catalysis oxidation furfurol reaction production maleic acid.
In one embodiment, the solid supported type metal porphyrin catalyst is that metalloporphyrin is combined with molecular sieve carrier Obtain afterwards.
In one embodiment, the molecular sieve carrier is any one in MCM-41, SBA-15, ZSM-5.
In one embodiment, the catalyst is with the mass ratio of substrate：1:15~1:3.
In one embodiment, the addition of catalyst is：The catalyst of 20-100mg is added per 0.282g furfurals.
In one embodiment, methods described also includes：After catalysis oxidation furfurol reaction terminates, will catalysis by filtering Agent is separated, and catalysis oxidation furfurol reaction is re-used for after washing, drying.
In one embodiment, the reaction temperature of the catalysis oxidation is 70-120 DEG C, and the reaction time is 3-12h, is applied Plus reaction pressure be 0.2-1.2MPa.
In one embodiment, the reaction temperature of the catalysis oxidation is 90-110 DEG C, and the reaction time is 4-5h, is applied Reaction pressure be 0.8-1.2MPa.
In one embodiment, the method that the catalysis oxidation furfural prepares maleic acid, specifically：
(1) solid supported type metal porphyrin and a certain amount of solvent (water) are added in polytetrafluoroethyllining lining, are added certain The furfural of amount, stainless steel cauldron is placed in by liner, is passed through oxygen and is reacted as oxidant, and the addition of catalyst is 20-100mg, reaction temperature is 70-120 DEG C, and the reaction time is 3-12h, and the reaction pressure of applying is 0.2-1.2MPa, reaction knot Shu Hou, question response kettle is cooled to room temperature, lentamente discharges pressure therein to normal pressure；
(2) after step (1) terminates, catalyst is separated by filtering, is washed by alcohol, step is re-used for after drying (1) used in.
In step (2), the conversion ratio of measured furfural is 20.4%-95.6%, and the yield of maleic acid is 10%- 56.1%, be selectively：43.6%-76.1%, after catalyst circulates 5 times, catalyst performance about reduces by 2%.
In one embodiment, the structural formula of the metalloporphyrin is：
Wherein, R includes but is not limited to-H ,-Br ,-Cl ,-F ,-CH3、-OCH3、-COOCH3；M represent metallic element Fe, Mn, Co, Cu, Zn or Ni.
In one embodiment, the metalloporphyrin is metalloporphyrin iron, and R is-Br.
Second object of the present invention is to provide a kind of preparation method of solid supported type metal porphyrin catalyst, the solid-carrying type Catalysis of metalloporphyrin agent is obtained after metalloporphyrin is combined with molecular sieve carrier；Methods described is by a certain amount of molecular sieve Carrier mixes with DMF solution, and heating stirring is uniform to solid particle dispersions for a period of time, and metalloporphyrin is slowly added dropwise thereto DMF solution, continues to react a period of time, is cooled to room temperature, suction filtration, and it is colourless to filtrate wash filter cake with solvent, removing carrier table Weaker porphyrin part is adsorbed in face, and tan product is obtained after drying.
In one embodiment, the molecular sieve carrier is any one in MCM-41, SBA-15, ZSM-5.
In one embodiment, the structural formula of the metalloporphyrin is： Wherein, R includes but is not limited to-H ,-Br ,-Cl ,-F ,-CH3、-OCH3、-COOCH3；M represents metallic element Fe, Mn, Co, Cu, Zn Or Ni.
In one embodiment, the metalloporphyrin is metalloporphyrin iron, and R is-Br.
In one embodiment, the preparation of the MCM-41：By template cetyl trimethylammonium bromide (CTAB) It is dissolved in deionized water, stirring a period of time, is added thereto to tetraethyl orthosilicate (TEOS), and use NH3·H2O (28wt%) Regulation solution PH continues to stir a period of time to 10.5, and coagulant liquid is transferred in crystallizing kettle into crystallization 24h at 105 DEG C, filtering, Washing, alcohol is washed, and is dried, and gained solid is put into Muffle furnace and is calcined, and obtains MCM-41 molecular sieves.
In one embodiment, the preparation of the SBA-15：With P123 as template, it is dissolved in deionized water, At room temperature stirring a period of time, the HCl solution of 2mol/L is added thereto to, and is added in mixed liquor by silicon source of TEOS, after Continuous reaction 22h, crystallization 24h in crystallizing kettle is transferred to by mixed liquor, and filtering, washing, alcohol is washed, dried, gained solid particle is put Template agent removing is removed in calcining in entering Muffle furnace, finally gives SBA-15 carriers.
In one embodiment, the preparation of the ZSM-5：TPAOH (TPAOH) is dissolved in deionized water In, stirring a period of time, silicon source TEOS is added, solution PH is adjusted with NaOH, continue to stir 24h, resulting solution is added to crystalline substance Change in kettle, crystallization 24h, filtering, are washed at a certain temperature, and alcohol is washed, and are dried, and finally gained solid is put into Muffle furnace and is forged Burn, obtain ZSM-5 samples.
In one embodiment, the preparation of the metalloporphyrin iron, is carried out in the steps below：
(1) synthesis of porphyrin part (T (p-R) PP)：The a certain amount of benzaldehyde with different para-orientating groups is taken, third is added Acid is heated to backflow as solvent in oil bath pan, then to the propionic acid solution that pyrroles is slowly added dropwise in mixed liquor, reacts 1h, Room temperature is cooled to, refrigerator is put into and is stood overnight, suction filtration obtains crude product.Crude product is purified using column chromatography method, is launched Agent is dichloromethane/chloroform.Wherein R includes-H ,-Br ,-Cl ,-F ,-CH3、-OCH3、-COOCH3This several substituted radical.
(2) preparation of metalloporphyrin iron (FeT (p-R) PP)：Synthesized porphyrin part in a certain amount of step (1) is taken to be dissolved in In DMF, backflow is heated in oil bath pan, FeCl is dividedly in some parts thereto2·4H2O, continues to react a period of time, and by subtracting Press the method for distillation that solvent is evaporated off, gained solid is immersed in deionized water overnight, suction filtration, washing is colourless up to filtrate, obtains The ferriporphyrin of brown.
In one embodiment, the solid supported type metal porphyrin catalyst is that (FeT (p-R) PP) is immobilized to molecular sieve On carrier MCM-41, SBA-15 or ZSM-5, FeT (p-R) PP/MCM-41, FeT (p-R) PP/SBA-15 or FeT are obtained (p-R)PP/ZSM-5。
The present invention has the following advantages that and effect relative to prior art：
(1) catalyst that the present invention is used is solid supported type metal porphyrin, and maleic acid is not only converted into furfural to be had well Catalytic effect, and reaction condition is gentle, the energy consumption needed for greatly reducing prior art.
(2) carrier selected by catalyst of the invention has special structure, can for reaction provide one it is good micro- Environment, so as to improve the yield and selectivity of maleic acid.According to the method for the present invention, the conversion ratio of furfural is 20.4%- 95.6%, the yield of maleic acid is 10%-56.1%, and selectivity is 43.6-76.1%；After catalyst circulates 5 times, catalyst performance 2% can about be reduced.
(3) active site of the catalyst that the present invention is used is metalloporphyrin, and it possesses good property, more gentle Reaction condition under realize furfural to the Efficient Conversion of maleic acid.
(4) solid supported type metal porphyrin catalyst of the invention is heterogeneous type, and reaction can by simple filtering after terminating By catalyst reclaim and for next secondary response in, and repeatedly circulate after still have good catalytic effect, embody green The policy of chemistry.
Brief description of the drawings
Fig. 1 is the reaction scheme for preparing maleic acid of the invention.
Fig. 2 is the yield figure of different carriers types of metals porphyrin catalyst catalysis furfurol reaction in embodiment 1.
Fig. 3 is that solid supported type metal porphyrin catalyst is catalyzed the yield figure of furfurol reaction at different temperatures in embodiment 2.
Fig. 4 is that solid supported type metal porphyrin catalyst is catalyzed the yield figure of furfurol reaction under different time in embodiment 3.
Fig. 5 is that solid supported type metal porphyrin catalyst is catalyzed the product of furfurol reaction under different catalysts consumption in embodiment 4 Rate figure.
Fig. 6 is that solid supported type metal porphyrin catalyst is catalyzed the yield of furfurol reaction under differential responses pressure in embodiment 5 Figure.
Specific embodiment
With reference to embodiment, the invention will be further described, but embodiments of the present invention not limited to this.
Embodiment 1
(1) 50mg solid supported type metal porphyrin catalyst FeT (p-R) PP/SBA-15 (wherein R is-Br) is weighed in polytetrafluoro In ethene liner, in addition 4mL deionized waters；
(2) the carrier S BA-15 in step (1) is changed into MCM-41, ZSM-5；
(3) weigh in 0.282g furfurals addition step (1), the reaction system of step (2), polytetrafluoroethyllining lining is put into Stainless steel cauldron, is heated to 90 DEG C under magnetic stirring, is passed through oxygen, applies the reaction pressure reaction 6h of 1MPa, reaction knot Oxygen bottle valve is closed after beam, after question response kettle is cooled to room temperature, gas slowly therein is released；
(4) reaction solution in 50 μ L steps (3) is pipetted with liquid-transfering gun, 5mL is settled to deionized water, use high performance liquid chromatography Instrument determines the yield of maleic acid.
After measured, as a result as shown in Fig. 2 catalyst oxygen obtained by with SBA-15, MCM-41, ZSM-5 as carrier Change furfural, the yield of maleic acid is respectively 38%, 27.8%, 22.3%, and selectivity is respectively 70.8%, 67.6%, 67%.
The solid-carrying type ferriporphyrin catalyst that inventor employs different substituents is compared, including-H ,-Br ,-Cl ,- F、-CH3、-OCH3、-COOCH3、-SO3Na, it is found that when it is-Br to replace base, catalytic effect is best, specific experiment tables of data 1.
The solid-carrying type ferriporphyrin catalysis oxidation furfural of the different substituents of table 1 prepares the result of maleic acid
Note：Reaction condition：Furfural, 0.282g；Catalyst, 50mg；H2O, 4mL；90℃；6h；O2, 1MPa.
In addition, inventor has attempted iron, manganese, cobalt, copper, zinc, six kinds of metals of nickel are with porphyrin ligands and anti-for being catalyzed Ying Zhong, specific experiment data such as table 2.
The solid-carrying type porphyrin catalysis oxidation furfural of the not same metal of table 2 prepares the experimental result of maleic acid
Note：Reaction condition：Furfural, 0.282g；Catalyst, 50mg；H2O, 4mL；90℃；6h；O2, 1MPa.
Additionally, inventor is investigated the influence to reacting without immobilized metalloporphyrin；Although not immobilized metal porphin Quinoline has certain catalytic activity, but catalyst stability is poor, is oxidized easily degraded；And work as using non-immobilized metal porphin During quinoline, reaction system is not heterogeneous, is difficult to realize and recycles, and can cause the waste of catalyst.
Embodiment 2
(1) 50mg solid supported type metal porphyrin catalyst FeT (p-R) PP/SBA-15 (wherein R is-Br) is weighed in polytetrafluoro In ethene liner, in addition 4mL deionized waters；
(2) weigh in the reaction system that 0.282g furfurals add step (1), polytetrafluoroethyllining lining is put into stainless steel anti- Kettle is answered, 70-120 DEG C is heated under magnetic stirring, be passed through oxygen, apply the reaction pressure reaction 6h of 1MPa, after reaction terminates Oxygen bottle valve is closed, after question response kettle is cooled to room temperature, gas slowly therein is released；
(3) reaction solution in 50 μ L steps (2) is pipetted with liquid-transfering gun, 5mL is settled to deionized water, use high performance liquid chromatography Instrument determines the yield of maleic acid.
After measured, as a result as shown in figure 3, when reaction temperature be 70 DEG C, 80 DEG C, 90 DEG C, 100 DEG C, 110 DEG C, 120 DEG C when, The yield of maleic acid is respectively 9.8%, 23.1%, 38%, 48.3%, 37.1%, 35.3%, selectively respectively 48%, 60.5%th, 70.8%, 76.1%, 50.1%, 43.6%.
Embodiment 3
(1) 50mg solid supported type metal porphyrin catalyst FeT (p-R) PP/SBA-15 (wherein R is-Br) is weighed in polytetrafluoro In ethene liner, in addition 4mL deionized waters；
(2) weigh in the reaction system that 0.282g furfurals add step (1), polytetrafluoroethyllining lining is put into stainless steel anti- Kettle is answered, 100 DEG C are heated under magnetic stirring, be passed through oxygen, apply the reaction pressure reaction 3-8h of 1MPa, reaction is closed after terminating Oxygen bottle valve is closed, after question response kettle is cooled to room temperature, gas slowly therein is released；
(3) reaction solution in 50 μ L steps (2) is pipetted with liquid-transfering gun, 5mL is settled to deionized water, use high performance liquid chromatography Instrument determines the yield of maleic acid.
After measured, as a result as shown in figure 4, between when reacted be respectively 3h, 4h, 5h, 6h, 7h, 8h when, the yield of maleic acid Respectively 35.7%, 41.6%, 44.1%, 48.3%, 45%, 40.3%.Selectivity be respectively 76.4%, 78%, 79.5%, 76.1%th, 65.7%, 49%.
Embodiment 4
(1) 30mg, 40mg, 50mg, 60mg, 70mg, 80mg solid supported type metal porphyrin catalyst FeT (p-R) PP/ are weighed SBA-15 (wherein R be-Br) in polytetrafluoroethyllining lining, in adding 4mL deionized waters；
(2) weigh in the reaction system that 0.282g furfurals add step (1), polytetrafluoroethyllining lining is put into stainless steel anti- Kettle is answered, 100 DEG C are heated under magnetic stirring, be passed through oxygen, apply the reaction pressure reaction 6h of 1MPa, reaction is closed after terminating Oxygen bottle valve, after question response kettle is cooled to room temperature, gas slowly therein is released；
(3) reaction solution in 50 μ L steps (2) is pipetted with liquid-transfering gun, 5mL is settled to deionized water, use high performance liquid chromatography Instrument determines the yield of maleic acid.
After measured, as a result as shown in figure 5, when the consumption of catalyst be respectively 30mg, 40mg, 50mg, 60mg, 70mg, During 80mg, the yield of maleic acid is respectively 25.2%, 37.6%, 48.3%, 56.1%, 50.3%, 45.7%, and selectivity is respectively It is 45.8%, 64.2%, 76.1%, 73.8%, 69.9%, 62%.
Embodiment 5
(1) 60mg solid supported type metal porphyrin catalyst FeT (p-R) PP/SBA-15 (wherein R is-Br) is weighed in polytetrafluoro In ethene liner, in addition 4mL deionized waters；
(2) weigh in the reaction system that 0.282g furfurals add step (1), polytetrafluoroethyllining lining is put into stainless steel anti- Kettle is answered, 100 DEG C are heated under magnetic stirring, be passed through oxygen, apply 0.2,0.4,0.6,0.8,1,1.2MPa reaction pressure Reaction 6h, reaction closes oxygen bottle valve after terminating, and after question response kettle is cooled to room temperature, gas slowly therein is released；
(3) reaction solution in 50 μ L steps (2) is pipetted with liquid-transfering gun, 5mL is settled to deionized water, use high performance liquid chromatography Instrument determines the yield of maleic acid.
After measured, as a result as shown in fig. 6, when reaction pressure be 0.2MPa, 0.4MPa, 0.6MPa, 0.8MPa, 1MPa, During 1.2MPa, the yield of maleic acid is respectively 10%, 18.2%, 33%, 45.1%, 56.1%, 55%.Selectivity is respectively 50.1%th, 66.9%, 73.4%, 75.5%, 73.8%, 70.7%.
After the reaction of embodiment 5 terminates, the catalyst under optimum condition is isolated by filtration out, cleans drying, then put into Optimal experiment condition in embodiment, for computing repeatedly.Through experimental calculation, solid supported type metal porphyrin is recycled 5 times, Malaysia The yield of acid still up to 54%.
Embodiment 6：The preparation of solid supported type metal porphyrin catalyst
Solid supported type metal porphyrin catalyst is obtained after metalloporphyrin iron is combined with molecular sieve carrier；Specifically by one Quantitative molecular sieve carrier mixes with DMF solution, and heating stirring is uniform to solid particle dispersions for a period of time, thereto slow drop Plus the DMF solution of metalloporphyrin, continue to react a period of time, be cooled to room temperature, suction filtration, washed with solvent filter cake to filtrate without Color, removes carrier surface and adsorbs weaker porphyrin part, and tan product is obtained after drying.
The preparation of metalloporphyrin iron, is carried out in the steps below：
(1) synthesis of porphyrin part (T (p-R) PP)：The a certain amount of benzaldehyde with different para-orientating groups is taken, third is added Acid is heated to backflow as solvent in oil bath pan, then to the propionic acid solution that pyrroles is slowly added dropwise in mixed liquor, reacts 1h, Room temperature is cooled to, refrigerator is put into and is stood overnight, suction filtration obtains crude product.Crude product is purified using column chromatography method, is launched Agent is dichloromethane/chloroform.Wherein R includes-H ,-Br ,-Cl ,-F ,-CH3、-OCH3、-COOCH3This several substituted radical.
(2) preparation of metalloporphyrin iron (FeT (p-R) PP)：Synthesized porphyrin part in a certain amount of step (1) is taken to be dissolved in In DMF, backflow is heated in oil bath pan, FeCl is dividedly in some parts thereto2·4H2O, continues to react a period of time, and by subtracting Press the method for distillation that solvent is evaporated off, gained solid is immersed in deionized water overnight, suction filtration, washing is colourless up to filtrate, obtains The ferriporphyrin of brown.
Molecular sieve carrier is MCM-41, SBA-15 or ZSM-5, and the solid supported type metal porphyrin catalyst for obtaining is respectively FeT(p-R)PP/MCM-41、FeT(p-R)PP/SBA-15、FeT(p-R)PP/ZSM-5。
Above-described embodiment is the present invention preferably implementation method, but is not the limitation to embodiments of the present invention, herein In field, other any changes, modifications done without departing from principle of the invention and within spiritual, combination, replacement, simplification, Belong to equivalent substitute mode, be included within the protection domain of the claims in the present invention.

Claims (10)

1. a kind of method that catalysis oxidation furfural prepares maleic acid, it is characterised in that methods described is using solid supported type metal porphin Quinoline catalyst, furfural is substrate, oxygen as oxidant, catalysis oxidation furfurol reaction production maleic acid；The solid supported type metal Porphyrin catalyst is obtained after metalloporphyrin is combined with molecular sieve carrier.
2. method according to claim 1, it is characterised in that the molecular sieve carrier is MCM-41, SBA-15, ZSM-5 In any one.
3. method according to claim 1, it is characterised in that the structural formula of the metalloporphyrin is：
Wherein, R includes but is not limited to-H ,-Br ,-Cl ,-F ,-CH3、-OCH3、- COOCH3；M represents metallic element Fe, Mn, Co, Cu, Zn or Ni.
4. method according to claim 1, it is characterised in that the metalloporphyrin is metalloporphyrin iron.
5. method according to claim 1, it is characterised in that the reaction temperature of the catalysis oxidation is 70-120 DEG C, instead It is 3-12h between seasonable, the reaction pressure of applying is 0.2-1.2MPa.
6. method according to claim 1, it is characterised in that the catalyst is with the mass ratio of substrate：1:15~1: 3。
7. method according to claim 1, it is characterised in that methods described also includes：Catalysis oxidation furfurol reaction terminates Afterwards, catalyst is separated by filtering, by washing, dry after be re-used for catalysis oxidation furfurol reaction.
8. a kind of preparation method of solid supported type metal porphyrin catalyst, it is characterised in that the solid supported type metal porphyrin catalyst Obtained after metalloporphyrin is combined with molecular sieve carrier；Methods described is by a certain amount of molecular sieve carrier and DMF solution Mixing, heating stirring is uniform to solid particle dispersions for a period of time, and the DMF solution of metalloporphyrin is slowly added dropwise thereto, continues Reaction a period of time, it is cooled to room temperature, suction filtration, it is colourless to filtrate wash filter cake with solvent, removes carrier surface and adsorbs weaker Porphyrin part, obtains tan product after drying.
9. the solid supported type metal porphyrin catalyst that claim 8 methods described is prepared.
10. the application of the solid supported type metal porphyrin catalyst described in claim 9.
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